west virginia department of environmental protection

Appendix B.5

Carbon Analysis 

for

 PM2.5 and Regional Haze

Promoting a healthy environment.

WV Regional Haze SIP 
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WV Regional Haze SIP 
Patricia Brewer1, 

Johann Engelbrecht2, Roger Tanner3, 

Scott Reynolds4, John Calcagni5

1VISTAS

2Desert Research Institute

3Tennessee Valley Authority

4South Carolina Department of Health and Environmental Co

5Environmental Protection Agency 

VISTAS Special Monitoring Stu

Carbon Analyses for PM2.5 and 

WV Regional Haze SIP 
Presentation Objectiv

• VISTAS Data Analysis • Special Monitoring Studies

• Carbon Studies: C14 isotope, Positiv

Factorization, and Chemical Mass Ba

WV Regional Haze SIP 
Areas with Poorest Visibility are similar to PM2.5 Non-attainm

WV Regional Haze SIP 
IMPR

Federa

Class 

BRET1

BRIG1

CACR1

CADI1

CHAS1

COHU1

DOSO1

EVER1

GRSM1

HEGL1

JARI1

LIGO1

MACA1

MING1

OKEF1

ROMA1

SAMA1

SHEN1

SHRO1

SIPS1

SWAN1

UPBU1

WV Regional Haze SIP 
Average Extinction for 20% Haziest Days

New IMPROVE Algorithm 

2000-2004

VISTAS coastal VISTAS inland non-VISTAS

0

50

100150200250300

SWAN

ROMA

OKEF

EVER

CHAS

SAMA

DOSO

SHEN

JARI

LIGO

SHRO

GRSM

COHU

SIPS

MACA

BRIG

BRET

MING

HEGL

UPBU

Extinction (Mm -1) 

Sulfate dominates the 20% Haziest Days at VISTAS Class I a

WV Regional Haze SIP 
Average Extinction for 20% Best Days

New IMPROVE Algorithm

2000-2004

0

102030405060

SWAN

ROMA

OKEF

EVER

CHAS

SAMA

DOSO

SHEN

JARI

LIGO

SHRO

GRSM

COHU

SIPS

MACA

BRIG

BRET

MING

HEGL

UPBU

CACR

VISTAS coastal VISTAS inland non-VISTAS

Extinction (Mm-1)

Sulfate also dominates the 20% Clearest Days at VISTAS Clas

WV Regional Haze SIP 
Natural Conditions -- New IMPROVE Algorithm 

0

1020304050

Great Smoky Mtns

Shenandoah

Cape Romain

Okefenokee

Everglades

Breto

Left = B20%; Center = Average; Right = W20%

*Breton based on 2001Q2-2002Q1 & 2002Q4-2003Q3 

bext (Mm-1)

WV Regional Haze SIP 
Monitoring Objective

 Identify sources of organic carbon

 Use high volume samplers with PM2.5 he

quartz filters at 5 sites

 Samples collected April 2004 – May 2005 Analyses by Desert Research Institute  Select 250 samples for carbon analysis (5 

50 samples per site including field and lab 

 Define carbon mass of each sample Characterize organic composition (GC/M Identify tracers of primary sources of carb

(Chemical Mass Balance and Positive MaFactorization)

WV Regional Haze SIP 
Monitoring Objectives

 Identify sources of organic carbon

 For same samples, characterize C14

isotope and ratio of modern to fossil c

 Analyses by Woods Hole Oceanographi

Institute’s National Oceanographic ScienAccelerator Mass Spectrometry (NOSAM

 Sources of modern carbon: vegetativ

emissions, wood burning, agriculturaburning, cooking

 Sources of fossil carbon: gasoline, d

oil

WV Regional Haze SIP 
CLASS 1 URBAN

Great Smoky Mtns.

Cape Romain

Raleigh

VISTAS Carbon Study Sites

Shenandoah

Mammoth Cave

WV Regional Haze SIP 
Sources of Organic Carb

Lessons Learned

 Modern carbon fraction seldom <0.60, 

usually >0.70 

 Higher modern carbon at forested sites 

(GRSM and MACA) than coastal (ROMAurban (MILL) sites

 Higher total carbon and higher total PM2.5 at 

urban site correspond to lower modern carb

 No clear seasonal trends in modern carb

 Hypothesize that greater wood burning in w

months and greater vegetative emissions in spring/summer

WV Regional Haze SIP 
Apr 2004 

WV Regional Haze SIP 
Fraction Modern Carbon vs. Aerosol Carbo

Cape Romain, All Seasons

y = 0.045x + 0.556

R2 = 0.422

0.300.400.500.600.700.800.901.00

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 

Aerosol C, 

μg/m3

Fraction Modern Carbon, fm

WV Regional Haze SIP 
WV Regional Haze SIP 
Great Smoky Mtns, All Seasons

y = 0.038x + 0.609

R2 = 0.1362

0.300.400.500.600.700.800.901.001.10

0.00 1.00 2.00 3.00 4.00 5.00 6.00 

Aerosol Carbon , μg/m3

Fraction Modern Carbon, f

m

Fraction Modern Carbon vs. Aerosol Carbo

WV Regional Haze SIP 
WV Regional Haze SIP 
Mammoth Cave, All Seasons

0.300.400.500.600.700.800.901.001.10

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 

Fraction Modern Carbon, f

m

Aerosol Carbon , μg/m3

Fraction Modern Carbon vs. Aerosol Carbo

WV Regional Haze SIP 
WV Regional Haze SIP 
Aerosol Carbon , μg/m3

Fraction Modern Carbon vs. Aerosol Carbo

Millbrook, All Seasons

0.300.400.500.600.700.800.901.001.10

0.00 2.00 4.00 6.00 8.00 10.00 

Fraction Modern Carbon, f

m

WV Regional Haze SIP 
WV Regional Haze SIP 
Shenadoah, All Seasons

y = 0.054x + 0.514

R2 = 0.434

0.300.400.500.600.700.800.901.001.10

0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 

Aerosol Carbon , μg/m3

Fraction Modern Carbon vs. Aerosol Carbo

Fraction Modern Carbon, f

m

WV Regional Haze SIP 
Monitoring Objective

 Positive Matrix Factorization applied t

cluster organic compounds. 

 Tracers identified for

 Biogenic Emissions Vegetative Burn Gasoline emissions Diesel emissions Crude Oil (Commercial Marine, seen at ROM

 Analyses incomplete: tracers still need to 

related back to total carbon to understanrelative importance

WV Regional Haze SIP 
Vegetative burnBiogenic EmissionsDiesel CrudeMotor vehicles

WV Regional Haze SIP 
WV Regional Haze SIP 
WV Regional Haze SIP 
WV Regional Haze SIP 
WV Regional Haze SIP 
Monitoring Objective

 Chemical Mass Balance analyses

 results to date from few samples analyze

Zheng, Ga Tech

 Chemical markers (profiles) for primar

carbon sources:

 Wood Combustion Gasoline emissions Diesel emissions Meat Cooking Vegetative detritus Other Organic Matter (unidentified primary so

plus secondary organics) 

WV Regional Haze SIP 
GT-CMB Results

0.001.002.003.004.005.006.00

ROMA 1-22-04 ROMA 4-10-04 GRSM1-22-04 GRSM 4-10-04 MACA 1-22-04 MACA 4-10-04 MILL1-22-04 MILL 4-10-04 SHEN 1-22-04 SHEN 

μg/m3

Diesel Gasoline Wood Combustion Meat Cooking Vegetative Detritus 

WV Regional Haze SIP 
Carbon Source Attributio

Lessons Learned

 CMB Results from samples analyzed 

Mei Zheng, Ga Tech

 In April samples from all sites, unidentif

component is largest fraction (>70%)

 Likely secondary, likely biogenic 

 Wood combustion is largest identified 

component in Jan samples, all sites

 Gasoline higher in Jan than Apr samp Diesel at all sites in Apr, not Jan samp

WV Regional Haze SIP 
Carbon Source Attributio

Lessons Learned

 CMB analyses together with C14 resu

indicate that modern carbon is more important than fossil carbon at Class areas and urban area sampled.

 Little seasonal variability in modern car

 wood burning vs biogenic

 Still need integration to understand sou

contributions

WV Regional Haze SIP 
Next Steps 

 Relate organic tracers used as PMF fac

larger population of organic compounds 

 Complete CMB organic analyses all sam Relate organic profiles to measured carb Integrate results with C14 analyses  Interpret source attribution for organic ca Integrate results with SOA production in 

CMAQ/CAMx air quality models

 Finalize project reports  Submit manucript for publication

WV Regional Haze SIP